USPTO Patents Application 10634351

®

Europeiachea Patontamt
European Patent Office
Office europeen dee brevets

© Publication number:

0 214 112

A2

®

EUROPEAN PATENT APPLICATION

© Application number 86870107.9
© Oateoffiling: 31.07.86

© mt a.*-. C 08 K 5/34

C 08 L 67/02, C 07 D 209/48

§ Priority: 01.08.85 US 761253 02.05.86 US 856384

©

Applicant: Monsanto Company

@ Date of publication of application :

Patent Department 800 North Lindbergh Boulevard

SL Louis Missouri 63167 (US)

11.03.87 Bulletin 87/11

© Designated Contracting States:

Inventor: Blrum, Gall Hubert

1015 Edge worth Drive

AT BE CH DE FR GB IT LI LU NL SE

Klrfcwood Missouri 63122 (US)

Jansen, Richard Francis

2663 Nahn Drive

St. Louis Missouri 63129 (US)

Mathls, Thomas Coleman

9354 hazelridge Drive

St. Louis Missouri 63126 (US)

©

Representative : Lunt. John Cooper et al

Monsanto Europe S.A. Patent Department Avenue de

Tervuren 270-272 Letter Box No 1

B-1150 Brussels (BE)

© Polyester compositions containing phthallmldoesters.

@ Certain phthalimidoesters are useful as plasticizers for
polyethylene terephthaiate. particularly for polyethylene tereprt-
thaiate molding compositions containing a reinforcing agent
and a nucleating agent.

Bundesdruckerei Berlin

0 214112

Description

POLYESTER COMPOSITIONS CONTAINING PHTHALIMIDOESTERS

Background of the Invention

This invention relates to polyester compositions. Particularly, the invention relates to polyethylene
terephthalate compositions containing certain phthalimidoesters, as plasticizers. and more particularly to
compositions for molding engineering thermoplastic parts.

Polyalkylene terephthalates have long been used for the manufacture of various molded articles. Such
polymers, particularly when combined with reinforcing materials and fillers such as glass fibers, are suitable for
the manufacture of engineered thermoplastic molded articles due to their high wear resistance, durability and
high dimensional accuracy. These good physical properties are most readily achieved by molding a
composition containing reinforcing material, under conditions under which the polyalkylene terephthalates
become partially crystalline.

Of the polyalkylene terephthalates, polyethylene terephthalate imparts preferred physical properties in the
molded article. However, polyethylene terephthalate is often not the material of choice for injection molding
usage because relatively high mold temperatures, e.g., 120°C to 140°C. must be utilized to ensure good
moldability and to obtain the desired crystallinity. Because of the high temperatures required, relatively long
molding times are necessary. These stringent processing conditions often prevent the use of polyethylene
lerephthalate for injection molding in spite of its high rigidity and good heat distortion temperature. Other
polyester polymers, particularly polybutylene terephthalate require shorter molding times and lower molding
temperatures because of their higher inherent rate of crystallization. However, these polymers are inferior to
polyethylene terephthalate in their physical properties, particularly in their heat distortion temperature.

Thus, it is desirable to produce a polyethylene terephthalate molding composition that will crystallize at
lower temperatures. This lowering of crystallization temperature must be accomplished without unduly
adversely affecting the physical properties of the molded articles. Additionally, any additive that improves
crystallization must have sufficiently low volatility so that it does not volatilize out of the composition at
elevated processing temperatures, and so that it does not cause deposits on the mold surfaces. The
phthalimidoesters of the invention reduce the molding time and temperatures of polyethylene terphthalate
compositions by improving and reducing the lower temperature at which crystallization occurs during cooling
of the melt. Furthermore, such phthalimidoesters also result in polyethylene terephthalate compositions with
low volatility, good physical properties, and high gloss.

Summary of the Invention
The present invention provides a polyester composition comprising:
35 (a) a polyethylene terephthalate having an intrinsic viscosity of at least about 0.4 deciliter/gram

measured as a 0.5% by weight solution in a 60:40 mixture of phenol and tetrachloroethane at 25° C; and
(b) a ptasticizer comprising phthalimidoester of the formula:

O

AO H

X-A-C-O-R

wherein X is phthalimido. dihydrophthalimido. tetrahydrophthalimido. or hexahydrophthalimido and where
4S A is alkylene, or substituted alkylene with from 1 to 18 carbon atoms and where R is alkyl, alkenyl.

substituted alkyl, or substituted alkenyl with from 4 to 20 carbon atoms, or

O
it

50 -R ! -O-C-A' -X f

where X' may be the same as or different than X and is phthalimido. dihydrophthalimido.
tetrahydrophthalimido or hexahydrophthalimido and where R' is alkylene. alkenylene. substituted
5 5 alkylene, or substituted alkenylene with from 2 to 20 carbon atoms and A' is alkylene. or substituted

alkylene with from 1 to 18 carbon atoms.
If the phthalimidoester is a monophthalimidoester, it is preferred that Ihe number of carbon atoms is A or R
total from 5 to 30 carbon atoms. And if the phthalimidoester is a diphthalimidoester, it is preferred that the
carbon atoms of A, R' and A* total from 4 to 36 carbon atoms.
qq It is preferred that the phthalimidoester be at least about 0.1% by weight of the polyethylene terephthalate.
In a preferred embodiment, the present invention comprises a polyester molding composition comprising:
(al from about 40 to about 95 parts by weight of a polyethylene terephthalate having an intrinsic
viscosity of at least about 0.4 deciliter/gram measured as a 0.5% weight solution in a 60:40 mixture of

10

20

25

30

2

0 214112

phenol and tetrachloroethane at 25° C;

(b) from about 0.1 to 15 parts by weight of a ptasticizer comprising a phthalimidoester as defined
above :

(c) from about 0.1 to about 10.0 parts by weight of a nucleating agent; and

(d) from about 5 to about 60 pans by weight of a reinforcing agent.

This invention also provides a molded, shaped article prepared from the polyester molding composition
described above.

This invention also provides a process for the preparation of polyester compositions wherein a polyethylene
terephthalate having an intrinsic viscosity of at least about 0.4, preferably at least about 0.6 deciliters per gram
is mixed with phthalimidoester as defined above, and homogenized in a melt.

Detailed Description of the Invention

The poryethylene terephthalate used in preparing the polyester compositions of the invention has an
intrinsic viscosity of at least about 0.4 deciliters per gram when measured as a 0.5<Vo by weight solution in a
60:40 mixture of phenol and tetrachloroethane at 25° C. It is preferred that the intrinsic viscosity should be
about 0.6 deciliters per gram and in some instances an intrinsic viscosity of about 1.0 or more deciliters per
gram may be desirable. As used herein, the term "polyethylene terephthalate" includes polyethylene
terephthaJate as well as polyethylene terephthalate copolymers and polymer blends containing polyethylene
terephthalate. provided the copolymer or polymer blend is at least about 60°/o by weight of polyethylene
terephthalate. Preferred copolymers include those in which a portion of the ethylene glycol is replaced by
other polyhydric alcohols, including, but not limited to, propylene glycol and butylene glycol, and in which a
portion of the terephthalic acid is replaced by other polyfunction^ carboxylic acids. Suitable polymer blends
include physical mixtures of polyethylene terephthalate with other polymers, particularly other polyesters. The
poryethylene terephthalate is used in the molding composition in an amount of from about 50 to about 95 parts
by weight, preferably about 60 to about 9 parts by weight.

The phthalimidoester of this invention comprise compounds of the genera! formula :

O

tr

X-A-C-O-R

where X is phthalimido, dihydrophthalimido, tetrahydrophthalimido , or hexahydrophthalimido. where A is
alkylene or substituted alkylene, with from 1 to 18 carbon atoms, preferably from 1 to 12 carbon atoms, and
more preferably, from 1 to 6 carbon atoms, and where R is alkyl, substituted alkyl, alkenyl, or substituted
alkenyl with from 4 to 20 carbon atoms preferably from 7 to 18 carbon atoms or

O
ii

fct-O-C-A'-X'

where X* may be the same as or different than X and is phthalimido. dihydrophthalimido, tetrahydrophthalimido
or hexahydrophthalimido and where R' is alkylene alkenylene. substituted alkylene. or substituted alkenylene
with from 2 to 20 carbon atoms, preferably from 2 to 1 0 carbon atoms and A' is alkylene or substituted alkylene
with from 1 to 18 carbon atoms, preferably from 1 to 12 carbon atoms, and more preferably, from 1 to 6 carbon
atoms.

If the phthalimidoester is a monophthalimidoester, it is preferred that the carbon atoms of A and R total
from 5 to 30 carbon atoms, more preferably from 8 to 28 carbon atoms. If the phthalimidoester is a
diphthalimidoester, it is preferred that the carbon atoms of A, R\ and A* total from 4 to 36 carbon atoms more
preferably from 6 to 28 carbon atoms.

In general, the phthalimidoester is present at least about 0.1 Wo by weight of the polyethylene terephthalate.
In a complete molding composition the amount of phthalimidoester ranges from about 0.1 to about 15 parts by
weight, preferably, from about 3 to about 10 parts by weight. These phthalimidoester compounds have
excellent compatibility with polyethylene terephthalate. However, the concentration of phthalimidoester
should be kept below a level at which incompatability may occur under the conditions to which the
composition will be exposed.

The phthalimidoesters of this invention can be prepared by any method known in the art. For example, U. S.
Patent No. 3,579,363 describes preparation of 2-ethylhexyl phthalimidoacetate by reacting potassium
phthalimide and 2-ethylhexyl a-chloroactate. It is preferred that the phthalimidoesters be prepared by reacting
phthalic anhydride, dihydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, or
mixtures thereof with either an amino acid or a lactam to form the precursor phthalimidocarboxylic acid which
is further reacted with an alcohol to form the phthalimidoester. For sake of simplicity, preparation of the
phthalimidoester will be discussed in terms of phthalic anhydride starting material, but the discussion also
applies to the hydrogenated phthalic anhydrides.

0 214112

When an amino acid is used, the phthalimidoester may be prepared in a two-step reaction. In the first step,
the amino acid is reacted with phthalic anhydride, usually in the presence of a solvent, such as toluene, xylene,
or diethylbenzene. to produce the precursor phthalimidocarboxylic acid. In the second step, this Intermediate
is esterified by reaction with an appropriate alcohol, preferably in the presence of an esterification catalyst,
5 such as stannous oxalate or other esterification catalyst, and preferably in the presence of an entralner. which
removes water released by the esterification reaction, either by reacting with the water or by forming an
azeotrope to remove the water from the reaction mixture. A suitable entrainer Is diethyl benzene.

The phthalimidoester may also be prepared in a single step by mixing phthalic anhydride, the amino acid, the
alcohol, a catalyst, if desired, and a solvent, if desired, and maintaining the reaction mixture at reflux to remove
10 the water as it evolves. Excess alcohol can be used as the solvent and as an entrainer. After the reaction Is
complete, unreacted alcohol can be removed by steam stripping, which also insolubilizes the stannous oxalate
catalyst for easy removal.

Similarly, either a one-step or two-step process can be used with lactams. The one step process is preferred
with either amino acids or lactams, because of simplicity, and the ability to avoid introducing a solvent to the
15 reaction mixture. Additionally, if a lactam is used, the reaction proceeds at a higher rate if a one-step process Is
used.

Any amino acid can be used as a starting material, provided it does not contain substituents that interfere
with formation of the phthalimidoester, that render the resulting phthalimidoester incompatible with the
polyethylene terephthalate. or that render it ineffective. Examples of suitable amino acids include glycine,

20 a-alanine, fj-alanine, aminodecanoic acid, methionine, 3-aminobutyric acid, 6-aminocaproic acid, isoleucine,
2-amino-4-methylpentanoic acid. 2-amino-3-phenylpropionic acid, 2-amino-3-methylbutyric acid, amlnooctad-
ecanoic acid, or any other amino acid with a suitable alkylene or substituted alkylene group. A mixture of
suitable amino acids can also be used.
Any lactam can be used as a starting material, provided it does not contain susbtituents that interfere with

25 formation of the phthalimidoester or that render the resulting phthalimidoester incompatible with the
polyethylene terephthalate or that render it ineffective. Examples of suitable lactams include 2-pyrrolidone,
5-valerolactam, e-caprolactam, or any other lactam with asuitabie alkylene or substituted alkylene group.
Mixtures of suitable lactams or of lactams and amino acids can also be used.
When referring to amino acids, lactams, and groups A and A*, the phrase alkylene or substituted alkylene is

30 meant to include both straight and branched chain groups as well as groups that contain substituents that do
not interfere with formation of the phthalimidoester, and that do not render the resulting phthalimidoester
incompatible with the poiyetheylene terephthalate or ineffective. Examples of noninterfering substituents
include ether and thioether groups.

If monohydric alcohols are used for esterification, monophthalimide compounds result. If dihydric alcohols

35 are used, diphthalimide compounds result. Any monohydric alcohol can be used, provided it has from 4 to 20
carbon atoms, preferably 7 to 18 carbon atoms, and does not contain substituents that interfere with formation
of the phthalimidoester or that render the resulting phthalimidoester incompatible with the polyethylene
terephthalate or ineffective. Examples of suitable monohydric alcohols include heptanol, octanol, nonanol,
decanol. undecanol. dodecanol. octadecanol, or any other suitable monohydric alcohol or mixture of

40 monohydric alcohols. Any dihydric alcohol can be used provided it has from 2 to 20 carbon atoms, preferably
from 2 to 10 carbon atoms, and does not contain susbtituents that interfere with formation of the
phthalimidoester or that render the resulting phthalimidoester incompatible with the polyethylene
terephthalate or ineffective. Examples of suitable dihydric alcohols include ethylene glycol, propylene glycol,
neopentyl glycol, 1.4-butylene glycol. 1,6-hexanediol, 1,12-dodecanediol, 2-butene-l ,4-diol, diethylene glycol,

45 tnethylene glycol, or other suitable glycols or glycol oligomers or mixtures of dihydric alcohols. When referring
to the alcohols, or to groups R and R\ the phrases alkyl, alkenyl. alkylene, substituted alkylene, alkenylene, and
substituted alkenylene are meant to include both straight and branched chain groups, as well as groups that
contain other substituents that do not interfere with formation of the phthalimidoester, or render the resulting
phthalimidoester either incompatible with the polyethylene terephthalate or inactive.

50 Mixtures of monohydric or dihydric alcohols can also be used, which will result in a product that is a mixture
of monophthatimidoester and diphthalimidoester.

Any nucleating agents suitable for use in polyalkytene terephthalate molding compositions may be utilized in
the molding compositions of the Invention. All that is required is that the nucleating agent promotes nucleatlon
of the polyalkylene terephthalate crystals. Most nucleating agents raise the upper temperature at which

55 crystallization of the polyethylene terephthalate occurs as the melt cools. Suitable nucleating agents Include
organic and inorganic nucleators.

Inorganic nucleating agents include calcium salts, such as calcium terephthalate, calcium titanate, calcium
pyrophosphate, calcium silicate, calcium benzoate, calcium oxide, calcium carbonate, calcium fluoride,
calcium aluminosilicate. and the like. Sodium salts, such as sodium silicate, sodium phenyl phosphate, and

60 sodium aluminosilicate may be used. Other inorganic nucleating agents include salts of other metals, such as
hthium. potassium, rubidium and cesium, as well as other inorganic compounds such as zinc borate and
zeolites.

One suitable class of inorganic nucleating agents include monovalent metal salts of oxides of carbon,
silicon, germanium, tin, and lead. The preferred oxides are those of carbon and silicon, with carbon oxides
65 such as carbonate and bicarbonate being particularly preferred. Preferred monovalent metals include lithium,

0 214 112

sodium, potassium, rubidium, and cesium, with lithium, sodium and potassium being preferred, and sodium
being particularly preferred.

Other suitable nucleating agents include the sodium or potassium, or other metal salts of hydrocarbon
carboxylic acids. One class of suitable carboxylic acids contains between 7 and 25 carbon atoms preferably
more than 12 carbon atoms. Representative of these carboxylic acids are fatty acids such as stearic s
pelargomc and behen.c acid. Additionally, salts of ethylenediaminetetraacetic acid may be suitable nucleating
egents. particularly the sodium salt. These carboxylic acid salts also include the sodium or potassium salts of
carboxyl containing organic polymers, either fully or partially neutralized, such as copolymers of olefins or
aromatic olefins with acrylic or methacrylic acids or maleic anhydride. These polymeric materials include for
example, the sod.um or potassium salt of ethylene methacrylic acid copolymers or styrene maleic anhydride w
copolymers, mclud.ng both wholly or partially neutralized salts of each. In the copolymers above the olefin or
aromatic olefin moiety ordinarily comprises 5CXVo to 980/ 0 by weight of the copolymer and preferably 800/o to
989*. An especially preferred polymeric material is the sodium salt of ethylene methacrylic acid copolymer
Also included are salts of oligomers of unsaturated fatty acids, particularly dimers and trimers of Cie fatty
acids, commonly known as "dimer acid" and *trimer acid." f5

A preferred class of nucleators. whether organic or inorganic, is alkali metal salts and mixed salts containing
alkali metals. Preferred alkali metals are sodium and potassium, with sodium being particularly preferred

In general, any suitable reinforcing agent can be used in the molding compositions of the invention The
reinforcing agent may optionally be treated with various coupling agents or adhesion promoters in a manner in
which is well known to those skilled in the art. Examples of suitable reinforcing agents include glass fibers &
carbon fibers and filaments, aramid fibers, alumina, feldspar, asbestos, talc, calcium carbonates clay carbon
black, quartz, novaculite and other forms of silica, galenite. bentonite, garnet, mica, saponite beideliite
titanium dioxide and titanate whiskers, aluminum, iron or nickel fibers, whiskers or platelets vermicutite'
calcium metasihcate. and the like. In particular, the preferred reinforcing agent is glass fiber more particularly
glass fibers, comprised of lime-aluminum borosilicate glass that is relatively sodium free, commonly known as 25
E glass. In some instances, it also may be desirable to use a mixture of reinforcing agents such as a mixture
of glass fibers and mica.

Other optional additives may be included in the compositions of the invention. For example the
compositions of the invention may also include a chain extender which helps to compensate for polyester
chains which are broken by hydrolysis with resulting molecular weight degradation. Such chain extenders 30
include, for example, carbod.imides and polyepoxides. Epoxy resins, which are preferred, include an epoxy
formed from bisphenot-A and giycidol ether or polyepoxides obtained by reacting ortho cresol novolac and
epichlorohydrin. Especially preferred polyepoxides are epoxy cresol novolac resins. If a chain extender is
used, it is preferred that about 0.1 to about 5 parts by weight be used. Other optional additives may include
rnpact modifiers, mold release agents, anti-static agents, coloring agents, such as pigments and dyes ^
thermal oxidative and light stabilizers, flame retardants and other additives known in the art

The molding compositions of the invention can be prepared and molded using any conventional or
well-known method. For example, in one suitable method the polyalkylene terephthalate and glass fiber are
placed into an extrusion compounder to produce molding pellets. In another procedure, the polyalkylene
terephthalate and glass are mixed by dry blending, then either milled and communited or extruded and 40
chopped. Alternatively, the ingredients can be mixed with the powdered or granular polyalkylene resin and
directly molded by inject»on or transfer molding techniques Ordinarily, it is desirable to thoroughly free the
ingredients from as much water as possible.

It is preferred that compounding be carried out to ensure that the residence time in the molding machine is
short; the temperature is carefully controlled; friction heat is utilized; and an intimate blend between the 4S
additives and the polyester resin is obtained.

Although it is not essential, best results are obtained if the ingredients are precompounded. pelletized and
then molded. Precompounding can be carried out in conventional equipment. For example, after predrying the
polyalkylene terephthalate. e.g., at 130 P C for three hours, a single screw extruder may be fed with a dry blend
of the polyester resin and the glass and whatever other additives may be used. Alternatively a twin-screw $&
extrusion machine can be fed with polyalkylene terephthalate, glass fiber and other additives at the feed port
In either case, a generally suitable extruder temperature will be about 230° C to 300" C.

The molding compositions of this invention can be molded in any equipment conventionally used for molding
engineering thermoplastic compositions, using conventional techniques.

The phthalimidoester compounds of this invention act to improve the crystallization of the polyethylene ss
terephthalates to wh.ch they are added by decreasing the temperature to which crystallization will continue
upon cooling of the hot melt. Although not intending to be bound by theory, it is believed that the
phthalimidoesters improve crystallization by increasing the molecular mobility of the polymer chain

Additionally, the phthalimidoesters of this invention result in improved melt flow and in improved
processab.l.ty of polyethylene terephthalate compositions, intended for molding or other applications As a 60
result the phthalimidoesters can also be considered to be a flow aid or processing aid for polyethylene
terephthalate.

Because the phthalimidoesters of this invention decrease the temperature at which crystallization occurs
good heat distortion temperatures (HDT). gloss and other physical properties can be obtained at a lower
molding temperature. Also, smaller amounts of nucleating agents may be used without any loss of nucleating 65

0 214112

effectiveness.

The compositions of this invention can be prepared using compounding techniques kncwn In the art. They
may either be precompounded and pelietized. or mixed and compounded as part of the molding process. It is
preferred to precompound and pelletize the composition prior to molding. Precompounding can be
5 accomplished with a single screw extruder, dual screw extruder, a roller mill, or any other method known to
one skilled in the art.

The following examples are illustrative of this invention and are not intended to limit its scope.

In the molding formulations of examples, the following components were used: the polyethylene
terephthalate (PET) used had an intrinsic viscosity of about 0.66 deciliters/gram; the indicated plasticlzer: as a
W nucleator. an ethylene/methacrylic acid (85/1 5 by weight) partially neutralized to a sodium salt, sold by duPont
under the tradename Surlyn 8660; as a chain extender, a polyglycidyl ether of orthocresolformaldehyde
novolac. sold by Ciba-Geigy Corporation, under the tradename Araldite ECN 1273; and 1/8-inch (0.3175 cm)
chopped glass strand, sold by Pittsburgh Plate Glass and designated as product type 3540. Compositions
were made using plasticizer at a concentration of 5<Vo by weight based on PET. This formulation, expressed as
a percentage of the full formulation is as follows:

% Plasticizer
Based on PET

20

I2L

PET 65.6
Plasticizer 3.4
Nucleator 0.67
25 Chain Extender 0.33

Glass 30.0

The dried components were mixed and extruded in a single screw extruder, with a die temperature of about

30 260 C. The extruded ribbon was cooled, chopped into pellets and dried overnight. The dried, pelietized
composition was injection molded into a family mold, at a die temperature of about 275° C and a mold surface
temperature of 110'X. The closed time was 30 seconds.

The molded parts were tested to determine heat deflection temperature (HOT) by holding the specimen at
two support points separated by five inches (12.7 cm), raising the temperature 2°C per minute, and applying a

35 »oad of 264 psi (1 .26 kPa) at the midpoint. The temperature at which deformation of the specimen reaches 0.01
inches (.0254 cm) is the HDT. This is in accordance with ASTM D648-82. Tensile strength and <Yo elongation
were determined using ASTM D638-82. Izod impact was determined using ASTM D256-81, except that
untouched test specimens were used. Volatility of the compound PET was determined by heating for 4 hours
at 175°C on a rotating rack in a forced draft oven.

jo The T P k of the composition was determined by placing a sample of a molded part into the sample container
of a differential scanning calorimeter, that had been heated to about 290° C. After 2 minutes, the sample
container was removed and covered with powdered dry ice to "quench" the sample. The quenched sample
was dessicated a minimum of 5 minutes, then returned to the calorimeter that had been cooled to room
temperature. The calorimeter was programmed for a 10°C per minute temperature increase under a nitrogen

45 atmosphere. An exotherm was observed between about 100° C and about 125° C. The T P k is the temperature at
which heat evolves most rapidly during this exotherm. The T P k gives an indication of the effectiveness of the
plasticizer at enhancing crystallization with a lower T P k indicating greater effectiveness.

Additionally, the per se volatility of the indicated plasticizer was determined by thermogravimetric analysis of
the neat plasticizer, under air atmosphere, using a thermobalance with a programmed temperature rise of

50 10' C per minute. The thermobalance produced a plot of weight loss versus temperature. From this plot, the
temperature at which volatility losses began was determined, as well as the weight percent loss at 300° C and
350 C.

EXAMPLE 1

55 This example illustrates the stepwise preparation of undecyl 3-phthalimidoproprionate by the initial
preparation and isolation of the precursor acid 3-phthalimidopropionic acid, followed by esterffication with
undecyl alcohol.

A 500 ml flask, equipped with a stirrer, thermometer, and water-separating condenser, was charged with 0.5
mole of fl-alanine and 170 ml of xylene. This mixture was stirred and the temperature maintained at 1 10° -120° C
60 as 0.5 moles of phthalic anhydride was added in portions over 50 minutes. Warming was continued at reflux
until water was no longer collected. The reaction mixture was then cooled to room temperature, filtered and
the solid washed with xylene and dried. The product was 3-phthalimidopropionic acid, with a melting point of
138' -146- C.

A 0.44 mole portion of the precursor acid, 0.5 moles of undecyl alcohol, 0.3g of stannous oxalate catalyst.
65 and 50 g of diethylbenzene entrainer were charged to the equipment described above. This mixture was

6

0 214112

warmed al 210 ; C. with pressure reduced to maintain reflux, until water was no longer collected The reaction

SK M 30 - "* - - — - ■**

EXAMPLE 2

Jil!^.!^^"" S,6P Pr ° dUC,i0n °' UndeCy ' * which a., the

ft LtinT^T' * quip f ed J as in Exam P |e 1 w « charged with 1.0 mole of phthalic anhydride 1 0 moles ot

EXAMPLE 3

orP^l^nT'l d6 , S . cribes . ,he s,e P wise Preparation of undecyl 6-phthalimidohexanoate by the initial
aicoho'.' 5 a " 0n °' PfeCUrSOr add ' 6 -P^anmidohexanolc acid, followed by este^icJon with

JZXHZ? f quipped as in Exam P ,e 1 was char 9 e ° with 0.76 moles of 6-aminohexanoic acid and 250 ml of
xylene. Th,s m.xture was stirred and the temperature was maintained at 1 15°C-120°C as 0 76 moles of ohZt
anhydr.de was added in portions over 25 minutes. The reaction mixture was warmed ?t reflu™ntH wa* was
no longer collected. More xylene was added to aid stirring when the mixture The
raac ton mixture was filtered, and the solid was washed with xylene and dried to gh^ an flK ^J^
6-phthal.m.dohexanoic acid with a melting point of 105° -110° C V

and SfnTn 'S" °' ^ precursor aci * 0 6 moles of undecyl alcohol. 0.5g of stannous oxalate catalyst

^V^TcST 6n,rainer W ! re Char9ed t0 ,he 6qUipmem desc * bed above - T ^ S
warmed at 210 C. with the pressure reduced to maintain reflux until water was no lonaer rnll.rflrt tkI

sssssar s,eam - s,ripped as in Exampie 1 and the p — sssras

EXAMPLE 4

This example describes the use of c-caprolactam and the simultaneous charging of all three react ant, .«
produce undecyl 6-phthalimidohexanoate. without isolation of the intermediate acid
annvdnTrZ 7" d Examp ' e 1 W3S charoed wi,n »•» ™les of e-caprolactam. 0.89 moles of phthalic

SSS S'l men^Tn 1 , T 0 " 0 '- ^ °' dieth " b — * This mixVure was 2£2Sf,

ira I ror 1 hour and then 0 7g of stannous oxalate catalyst was added and warmino was continued at ow r

was Soared Th 6 T fedUCed ,0 m8imain re,,UX - «* m0re 01 ^Z££S5Xi e2ng
was continued. The reaction mixture was steam-stripped as above and filtered resultino In «m7tu» m
approximately 95°/o undecyl 6-phthalimidohexanoate and 5 o/o other »SS

EXAMPLE 9

pr^SSr^mil! 0 '! 6 ?-' "T^" ' r ° m Ph,ha ' iC anh * dride - and °<=« a <"*yl alcohol by a

procedure sim.lar to that used m Example 1. except that the intermediate acid was not .solated from it*

reacon med.um betore i, was es.eritied. The product had a proton NMR spectrum consistent wl utS.o.i

to

15

20

P5

30

35

40

4$

EXAMPLE 5

th^h^o 3 -P rt htf ; alimi ^P ro P j onate was prepared by a procedure similar to that used in Example 1 except

T ^ W3S n0t IS0,ated before jt was esterified ^ ^tadecyl alcohol The Xucfhad a
proton NMR spectrum that was consistent with the desired structure.

EXAMPLE 6

a ^t 6Cyl 6 -P ht ^ ha,imidohex anoate was prepared from phthalic anhydride, c-caprolactam and octadecvl

K^K2S^ t0 that used ln Examp,e 4 The w has a —

EXAMPLE 7

-nJSSS? Jl^^^ i T i SSS2^r , ° ,rt ^ T P : ePar6d ,f0m Ph,haliC anhydride ' ""^noundecanoic acid.
notSed <££ flllZZSZ similar to that used in Example 1. except that the intermediate acid was

aesired structure P 3 PTO,0n NMR SpeC,rum ,hat w « '°™s<*"< with the

EXAMPLE 8 ff
uni n S 2 K Ph, !! alimid0 ^' ,rne,hy,thi0,bu,yra,e was P re P ared **" Phthalic anhydride DL-methion.ne and

Suture * eS,er ' ,,ed The pr0dUC ' had 8 pro,on NMR S P<"<™"> consistent with the desired

50

60

7

0 214112

structure.
EXAMPLE 10

A mixture of octadecyl and hexadecyl 4-phthalimidobutyrate was prepared from phthalic anhydride
5 4-aminobutyric acid, and tallow-derived Ci e- 1 8 alcohol by a procedure similar to that used in Example 1 except
that the intermediate acid was not isolated from the reaction mixture before it was esterified. The product had
a proton NMR spectrum consistent with the desired structure.

EXAMPLE 11

Undecyl 2-phthalimidopropionate was prepared from phthalic anhydride. DL-alanine, and undecyl alcohol by
a procedure similar to that used in Example 1, except that the intermediate acid was not isolated from Its
reaction medium before it was esterfied. The resultant product had a proton NMR spectrum consistent with
the desired structure.

EXAMPLE 12

A mixture of heptyf, nonyl, and undecyl 6-phthaJimidohexanoates was prepared from phthalic anhydride,
i.-caprolactam, and a mixture of about 300/o C 7 alcohol, about 40A'o C9 alcohol, and about 30^0 Cn alcohol, by
a procedure similar to that used in Example 4. The product had a proton NMR spectrum consistent with the
desired structure.

EXAMPLE 13

2-Ethylhexyl 6-phthaIimidohexanoate was prepared from phthalic anhydride, e-caprolactam and 2-ethylhexyl
alcohol by a procedure similar to that used in Example 4. The product had a proton NMR spectrum consistent
with the desired structure.

EXAMPLE 14

Dodecyl 6-phthalimidohexanoate was prepared from phthalic anhydride, E-caprolactam. and dodecyl
alcohol by a procedure similar to that used in Example 4. The product had a proton NMR spectrum consistent
with the desired structure.

EXAMPLE 15

Undecyl 2-phthallmldoacetate was prepared by adding 2.2 moles of undecyt alcohol to a suspension of 2
moles of 2-phthalimidoacetlc acid in xylene. The mixture was stirred and wanned, allowing xylene and the
water of reaction to distill until a pot temperature of 210°C was reached at a pressure of about 250 mm Hg.
Refluxing at this temperature was continued until water no longer was produced. The reaction mixture was
steam-stripped as above and filtered yielding a product having a proton NMR spectrum consistent with the
desired structure.

EXAMPLE 16

The di(3-phthalimldoproplonate) diester of 2,2-dimethyl-1,3-propanediol was prepared with phthalic
anhydride, p-alanine and the dihydric alcohol by a procedure similar to that used in Example 1 . The product had
a melting point of 158-162"C. and its proton NMR spectrum was consistent with the desired structure.

EXAMPLE 17

The di(6-phthalimldohexanoate) diester of 2.2-dimethyl-1,3-propanediol was prepared from phthalic
anhydride. 6-aminohexanoic acid, and the dihydric alcohol by a procedure similar to that used in Example 1
except that the intermediate acid was not isolated from its reaction medium before it was esterified. The
product had a proton NMR spectrum that was consistent with the desired structure.

50 EXAMPLE 18

The di(6-phthalimldohexanoate) diester of triethyleneglycol was prepared from phthalic anhydride,
{i-caprolactam, and triethyleneglycol by a procedure similar to that used in Example 4. The product was a clear
amber liquid having a proton NMR spectrum that was consistent with the desired structure.

55 EXAMPLE 19

Undecyl 6-tetrahydrophthalimidohexanoate was prepared from 1.2 moles of 1.2,3.6-tetrahydrophthallc
anhydride, 1.2 moles of e-caprolactam, and 1.56 of undecanol in a Miter flask equipped as In Example 1. The
mixture was warmed at 180° C under nitrogen for 1 V 2 hours and 07g of stannous oxalate catalyst was added.
The mixture was heated to 250° C for 3V 2 hours with the pressure reduced to maintain reflux. About 21 ml of

60 water was collected. The reaction mixture was then steam stripped at 175°C and 10 mm Hg for 2 hours,
followed by continued stripping without steam for V 2 hour. The mixture was filtered giving a clear yeHow liquid
product. The product had a proton NMR that was consistent with the desired structure.

The products of the synthesis examples above were formulated into polyethylene terephthaJate molding
compositions and were molded as described above. Various of the phthalimldoe stars were tested in groups

t¥ some of which were compared with similar compositions made using a mixture of Cm. Cie, and Cie N-alkyl*

75

25

30

35

JO

45

8

0 214112

SS^If ^T- W !. ,T . SA) - SOme Were com P ared ««" similar formulations using no pUsflctter The
propartles of the plastwizera and of the formulated PET are reported in Tables I mrouflh V beta.

9

0 214112

Co e

e u

o m •

U* CT

•h a

H

W iJ «j

flu «i r

«
o

o
u

cu

cu

CO

c

H

oq

c

o

04

13

.C

oa
c

<u
u

CO

o

*u <o ca
o ajQ

N 8 -t
U

CJ
0

M N H

00 >y

0000

.00000
» • • • «

CM CS CM CM CM

0

O

0

0

O

»n

m

m

0

O

CM

CM

CM

m

in

*»

at

Ox

as

1— 1

r- •

co w» m co
• • • • «

cn cm co cm cn

<t G OS Q CO

■H .-4 pH pi

CM CM CM CM CM

cj
o

m m 0 o

r- no
o o

r*» vO r*
000

>*

(0

CO cj

O 0

>A O

^» ^

«

X CO

CO

CO 0
O 0

u

t-3 O

V

0

N

X CO

«H

U

•H

CO

*J

CO

C /-v

CO

CO

«

0

000

1-J

cu

a

CT\ 00
00

00 VO

m o

CM CM

m h vo
»j n h

CO O CM

CJ
000

a ^

•H

C

CU •■H

1

in «

vO

CO

mom

cm <r vo

CM CM CM

o> 00 o

^ r»

1 1 1

CO CO CO

I s - <r vo

CM to CO
r» 00 r-«
s»

p

co m

<

10

0 214112

/-v|

O 6
o <J

o m •
d

W *i «|

SO

cn

00

CM

cn

o

•

•

*

•

•

o

o

o

o

o

M
4J
'«-*
4->
U
4J

CM

O

hi

cu

•H

c
H

c
o
I—*

w

cu

CM CM ~

oq
c

u

CO

c

*o a u

N £ —»

OX O

• •

«-i CM

o

Q

o

o

o

m

O

o

m

m

OS

»— »

VO

cn

«»

•k

m

o>

ox

ON

00

o\

»— 1

1— 1

VO

CM

CM

CM

*

•

•

•

CM

CM

CM

CM

CM

>

r- •

u

o

00

vO

o

O

O

CM

CM

CM

CM

o

a. pi

HI

cm

O i-

O

CM

o

>

H

09 O

r-»

0 0

wJ O

«

o

CO

>

(0 u
0 0

>-} o

o

N

H cn

*H

O

•H

(0

4-1

to

C ^"N

<fl

6)

•H O

(0

0

00 O

i-H

m3

CJ w

cn in

cn

I CM

o

O

o

Ox

OX

i

CM

r- »

cn

SO
CM

CJ
000

c ^

•H

-H C

x: o

O 4J

x: ^

X o
W 2

•o

3

CM
SO

1

<»

CO

lO

l-«

Ox

O

m

in

so

SO

c

O

I

CO
SO

00

<

CO
H

u

s

s
&

a

o

O

11

0214112

So s

o u

o m •

CU 10 S

no in no o o oo

<r vo qo r*. r-i >y

• ••••••

o o o o o o o

ca
v

OJ
O

41

0}

C

op
c
o

I— I

w

OS o o o vo o* o

H CS N M w « N

ca

OJ

c

4)
J-t

CO

o o o
a m o
in n h

o
o

in

ON O O ON
H CM

O O

o o

O m

ON O

— <N

O <0 i— i

n a *

H E J

^ <^ i-l i-» O O NO

O h h eg oj ^

03
<

o

o
H

e

o

CO vO
f— t I— I

CM CM

H O »J (NJ vO
(N (N h r- ^

(N (N (N N N

00 00

j* o o

m o m o o

• • • t •

CO in vO On r».

O O O ~ O

(0

(0 O

»— *

O 0

►J o

m

a

cn

O

>

to a

O o

1-3 o

at

N

cn

u

•H

CO

a C

ca

a *h u

<Q

0 QOo

i— <

m ag w

CU

CQ

cn o

ON 00

cn cn

CM CN|

vo cn m

ON ON ON

no cn
r*

m m o

CO ON ON

I NO

• CN

m

NO

cm

ceo
c w

^ c

32 £

O 4J

X 2

M 0

* * * *

•O iO t3 O

*H r** *H 'H *h r*»

3 13 3 3 I

o< o o» o* cr eo

•H t*» «H »H VO

CO

m

00

cn

m

00

cn

cn

cn

ON

u

c

S 2 2 I g

u

e

O

o

OS

12

0 214112

u o E
o m o

1-4 Ql

H «
W *J ^

Pu co oc(

E

co cm cm co

00 r-

• • » •

o o o o

m

<

oc

c

o

o

w

o

•

•

•

eu

CM

<N

r— »

w

4-1

u

**

u

a

/— s

o

•H

u

CO

fiu

a

41

O

O

o

*— 1

m

O

m

•<H

>t

m

CO

oc

•*

•

c

c

a\

o>

tu

H

Str

* •

o o
o

m
00

o

O <9 tO
N O.J3

f*. m c*i
CM »-»

00

CM

O
0

*J >T 00 (S <t

f-< r-< O
<N CM CM CM CM

U
0

I

o m m m m

O

a. ~

HI

cr»
o

o> o\ r*»
o ^ o

u

000
C w
•H

+i 4J

^-t c

01 -i-t

r o

On.

0 4J

00
CO
I

vO
CO

NT

I

in
m

I

00
NO

o

CO

m co

CO vO

oo
i »-»

CJ

u

at
c

E
CJ

x o

U2I —

ft)

c <

m 00 O C73

»-■ *- X H

a
o
o

13

0 214112

W

CQ
<

o m 01

H oc

w a

cu CO

90
CJ

U

4J

aj
o

cu

4)
i-H

•H
03

c

0)

04

a

o

w

•H
W

a

u

W

<U CO
O « H

n a •

o

o o o

O CM O
N N N

o

o

o

o

m

m

l-H

CN

cn

«k

«

a\

OS

i— •

FN

i-H \Q v*
• • •

cn ^ cn

0

i

m ^ %r

F* FH

CN CN CN

CJ
0

in

m

Oi o o o

*| FN M M

CJ
00 0

e >^

<— I C

2 O
a.

o jj

X o

w as

t t s
f f i

>o

O NO CO
CN <-• i-*
^ ^

<

CO CO

01

Ul

3

eg
w

CI

8"
H

§

o
as

In addition to the compositions discussed above, glass reinforced PET molding compositions were
prepared utilizing 2-ethythexyl 6-tetrahydrophthalimidohexanoate. 2-ethylhexyi 6-hexahydrophthaJimldohexa.

14

0 214112

^C^J^fJ T ? ! K° m 6 f ° h ° f theSe com P° sltions * « ™ld with a surface temperature of about
107C a^rbited equiva ent physical properties, while the two hydrogenated phthaJImldoeaters produced

SUPe ! ° TSA COntr0 ' indiCt,n9 equivalent or 0 reatcr crystaJteatton man that

The preceding examples are intended to illustrate the current Invention and not to limit Its scope.

Claims

1. A polyester composition comprising:

(a) a polyethylene terephthaJate having an intrinsic viscosity of at least about 04 deciliter/ aram
measured as a O.50/0 by weight solution in a 60:40 mixture of phenol and tetrachloroethane at 25'C;

(b) a plasticizer comprising phthalimidoester of the formula:

0

X-A-C-O-R

wherein X is phthalimido, dihydrophthalimldo. tetrahydrophthaiimldo. or hexahydrophthalirnkJo and

EEL- - 1 5? nt i 0r ! ubstituted a,R y ,ene <™ ' to 18 carbon atoms a^ ^vhere R ?Jfi
substituted alkyl. alkenyf, or substituted aJkenyl with from 4 to 20 carbon atoms or

O
it

R'-O-C-A'-X'

where X' is the same as or different than X and is phthalimido. dihydrophthalimldo. tetrahydrophthaJ-
^^ydrophthallmido and where R' Is aikylene, aJkenylene. substituted iSX^r
^ 8 "Tl 8 8 'Sntr 2 ,0 20 ^ «™ " « « or subsided 3$g£

*'th^ ^ Dh ^ M ^ -I*- - -bout 0.1* by weight

3. A polyester molding composition comprising-

visc 3 ^^ *aF? by W6i ° ht ° f a P Q **W*»* terephthaJate having an intrinsic

^°TL°L ! east * oul dec,Jiter/gram measured as a 0.5* weight solution In a 60:40 mixture of
phenol and tetrachloroethane at 25° C; w

forrnu[a° m *"* ™ *° " ^ °' 3 ^ sXic ^ comprising a phthalimidoester of the

O
it

X-A-C-O-R

15

20

25

40

45

wt! rl A fl ,ft d °' d ' h y drt >P h thal.m»do. tetrahydrophthalimido, or hexahydrophthalimido and
where A is aikylene, or substituted aikylene with from 1 to 18 carbon atoms and ^here R is a**
substituted alkyl, alkenyl. or substituted alkenyl with from 4 to 20 oJZT.XoLor *

O
ti

R'-O-C-A'-X

4. The composition of Claim 3, wherein A, A' and R* are individually aikylene. and R is allkyl

5. The composition of Claim 3. wherein the phthalimidoester comprises a monophthaiimidoester in

SO

55

(c) from about 0.1 to about 10.0 parts by weight of a nucleating agent: and

(d) from about 5 to about 60 parts by weight of a reinforcing agent.

65

15

0214112

which the total number of carbon atoms of A and R is from 5 to 30 carbon atoms

th. 6 ',I^ ^,™^ Si,i ^ °V Claim 3 - whBrein the Phthallmidoester comprises a diphthalimktoester In which
the total number of carbon atoms of A. FV and A' is from 4 to 36 carbon atoms

I ! c ° mp09l,, ° n * 3 - "*<>™ n *» nucleating agent Is selected from the sell of a dimer acid the
salt of a trimer eckJ or the salt of a mixture of a dimer and a trimer acid

wt o/I h !iZ*™ S]t H n « £ la lT 3 ' W !l ere ' n the nuclaa,,n ° a °ent ■» « copolymer consiating essentially of 85
wt o/o ethylene and 15 wt. <Vb methacryiic acid which has been partially neutralized l, «di« £LV
9 The composition of Claim 3. wherein the reinforcing agent is flberg^s ° n8

10. The composition of Claim 3, containing from about 0.1 to about 5 parts by weight of a chain extender

11. The composrtion of Claim 10. wherein the chain extender is polyepoxlde

least abou? 0.r mOn °' * Wherei " p0lye,nylene *WMe has an' intrinsic viscosity of at

13. The composition of Claim 3. wherein the polyethylene terephthelate comprises a mixta.™ «f
polyetheylene terephthalate and polybutylene terephthalate comprises a m.xture of

14. The composition of Claim 3, further comprising at least one additive selected from Imoact modifior,
flow promoters, coloring agents, flame retardants. coupling agents and stabilizers to vSm*X£
and light stabilization In effective amounts. •* • «* amowzers ror tnermel oxidative

15. A polyester molding composition, comprising:

JntSZ" FT? ^ X °J b0U J 95 partS ^ wei9M of Polyetheylene terephthalate having an Intrinsic
viscosity of at least about 0.4 deciliters per gram; minnsic

(b) from about 0.5 to about 5.0 parts toy weight of a nucleating agenf

(c) from about 5 to about 60 parts by weight of fiberglass- ~ "

formu^" 1 ab ° Ut 0 5 '° ab ° Ut " P8rtS " y Wei9W 01 a Plas,icizer com P riai ng » Phthalimdoester of the
O

0

ir

Ql^-A-C-O-R

If

«^f n a JI? le " e ^ fr ° m 1 10 12 ortQB atoms a ^whereHisalkyl.oralkeny.withfrom4to20

carbon atoms, or

O

O »

cr ^
ii

cibraioms 710 " 8 W alkeny ' ene ^ 2 10 10 Carb ° n a,0mS and A> ,s a,k y |ana 1 to 12

16. A polyester molding composition, comprising-

*£* m of a a b t°C irSfdK^gram! P °' ye,heyl8ne ,erePMhala,e ^ " ^
(b) from about 0.5 to about 5.0 parts by weight of a nucleating agent*
c from about 5 to about 60 parts by weight of fiberglass-

Jdjfrom about 0.5 to about 15 parts by weight of a plasticizer comprising a phthalimdoester of the

16

0214112

where A is elkylene or substituted alkylene with trom 1 to 12 carton atoms and where R is ilk*
substituted aft* alkenyl. or substituted alkenyt with from 4 to 20 carton etoms
17. A process for producing a phthalimldoester comprising reacting phthalic anhydride with a lactam in

w

15

20

25

30

35

40

45

SO

55

60

65

17